Glass compositions having high thermal and chemical stability and methods of making thereof

ABSTRACT

Described herein are alkali-free, boroalumino silicate glasses exhibiting desirable physical and chemical properties for use as substrates in flat panel display devices, such as, active matrix liquid crystal displays (AMLCDs). In accordance with certain of its aspects, the glasses possess good dimensional stability as a function of temperature.

CROSS-REFERENCE TO RELATED APPLICATION

This is a continuation of U.S. patent application Ser. No. 12/943,268 filed on Nov. 10, 2010, which is a divisional application of U.S. patent application Ser. No. 11/704,837, filed Feb. 9, 2007, now U.S. Pat. No. 7,833,919, which claims the benefit under 35 USC §119(e) of U.S. Provisional Application No. 60/772,600 filed Feb. 10, 2006, the contents of which in its entirety is hereby incorporated by reference.

BACKGROUND

The production of liquid crystal displays such as, for example, active matrix liquid crystal display devices (AMLCDs) is very complex, and the properties of the substrate glass are extremely important. First and foremost, the glass substrates used in the production of AMLCD devices need to have their physical dimensions tightly controlled. The downdraw sheet drawing processes and, in particular, the fusion process described in U.S. Pat. Nos. 3,338,696 and 3,682,609, both to Dockerty, are capable of producing glass sheets that can be used as substrates without requiring costly post-forming finishing operations such as lapping and polishing. Unfortunately, the fusion process places rather severe restrictions on the glass properties, which require relatively high liquidus viscosities.

In the liquid crystal display field, thin film transistors (TFTs) based on poly-crystalline silicon are preferred because of their ability to transport electrons more effectively. Poly-crystalline based silicon transistors (p-Si) are characterized as having a higher mobility than those based on amorphous-silicon based transistors (a-Si). This allows the manufacture of smaller and faster transistors, which ultimately produces brighter and faster displays.

One problem with p-Si based transistors is that their manufacture requires higher process temperatures than those employed in the manufacture of a-Si transistors. These temperatures range from 450° C. to 600° C. compared to the 350° C. peak temperatures employed in the manufacture of a-Si transistors. At these temperatures, most AMLCD glass substrates undergo a process known as compaction. Compaction, also referred to as thermal stability or dimensional change, is an irreversible dimensional change (shrinkage) in the glass substrate due to changes in the glass' fictive temperature. “Fictive temperature” is a concept used to indicate the structural state of a glass. Glass that is cooled quickly from a high temperature is said to have a higher fictive temperature because of the “frozen in” higher temperature structure. Glass that is cooled more slowly, or that is annealed by holding for a time near its annealing point, is said to have a lower fictive temperature.

The magnitude of compaction depends both on the process by which a glass is made and the viscoelastic properties of the glass. In the float process for producing sheet products from glass, the glass sheet is cooled relatively slowly from the melt and, thus, “freezes in” a comparatively low temperature structure into the glass. The fusion process, by contrast, results in very rapid quenching of the glass sheet from the melt, and freezes in a comparatively high temperature structure. As a result, a glass produced by the float process may undergo less compaction when compared to glass produced by the fusion process, since the driving force for compaction is the difference between the fictive temperature and the process temperature experienced by the glass during compaction. Thus, it would be desirable to minimize the level of compaction in a glass substrate that is produced by a downdraw process.

There are two approaches to minimize compaction in glass. The first is to thermally pretreat the glass to create a fictive temperature similar to the one the glass will experience during the p-Si TFT manufacture. However there are several difficulties with this approach. First, the multiple heating steps employed during the p-Si TFT manufacture create slightly different fictive temperatures in the glass that cannot be fully compensated for by this pretreatment. Second, the thermal stability of the glass becomes closely linked to the details of the p-Si TFT manufacture, which could mean different pretreatments for different end-users. Finally, pretreatment adds to processing costs and complexity.

Another approach is to slow the kinetics of the compaction response. This can be accomplished by raising the viscosity of the glass. Thus, if the strain point of the glass is much greater than the process temperatures to be encountered (e.g., if the strain point is ˜200-300° C. greater than the process temperatures for short exposures), compaction is minimal. The challenge with this approach, however, is the production of high strain point glass that is cost effective.

Described herein are alkali-free glasses and methods for making the same that possess high strain points and, thus, good dimensional stability (i.e., low compaction). Additionally, the glass compositions also possess all of the properties required for downdraw processing, which is important in the manufacturing of substrates for liquid crystal displays.

SUMMARY

In accordance with the purposes discussed above, the disclosed materials, compounds, compositions, articles, devices, and methods, as embodied and broadly described herein, are alkali-free, boroalumino silicate glasses exhibiting desirable physical and chemical properties for use as substrates in flat panel display devices, such as, active matrix liquid crystal displays (AMLCDs). In accordance with certain of its aspects, the glasses possess good dimensional stability as a function of strain point. Additional advantages will be set forth in part in the description that follows, and in part will be evident from the description, or may be learned by practice of the aspects described below. The advantages described below will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying figures, which are incorporated in and constitute a part of this specification, illustrate several aspects described below.

FIG. 1 shows the dependence of dimensional change, here labeled “compaction,” versus strain point for a series of glass compositions described herein heated at 600° C. for five minutes.

FIG. 2 shows the compaction behavior versus time of three glass samples given repeated heat treatments at a temperature of 600° C.

DETAILED DESCRIPTION

The materials, compounds, compositions, articles, devices, and methods described herein may be understood more readily by reference to the following detailed description of specific aspects of the disclosed subject matter and the Examples included therein and to the Figures.

Before the present materials, compounds, compositions, articles, devices, and methods are disclosed and described, it is to be understood that the aspects described below are not limited to specific synthetic methods or specific reagents (specific batch components), as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Also, throughout this specification, various publications are referenced. The disclosures of these publications in their entireties are hereby incorporated by reference into this application in order to more fully describe the state of the art to which the disclosed matter pertains. The references disclosed are also individually and specifically incorporated by reference herein for the material contained in them that is discussed in the sentence in which the reference is relied upon.

Throughout the description and claims of this specification the word “comprise” and other forms of the word, such as “comprising” and “comprises,” means including but not limited to, and is not intended to exclude, for example, other additives, components, integers, or steps.

As used in the description and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a composition” includes mixtures of two or more such compositions, reference to “an agent” includes mixtures of two or more such agents, reference to “the layer” includes combinations of two or more such layers, and the like.

“Optional” or “optionally” means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where the event or circumstance occurs and instances where it does not.

Certain materials, compounds, compositions, and components disclosed herein can be obtained commercially or readily synthesized using techniques generally known to those of skill in the art. For example, the starting materials and reagents used in preparing the disclosed compounds and compositions are either available from commercial suppliers or prepared by methods known to those skilled in the art.

Also, disclosed herein are materials, compounds, compositions, and components that can be used for, can be used in conjunction with, can be used in preparation for, or are products of the disclosed methods and compositions. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds may not be explicitly disclosed, each is specifically contemplated and described herein. For example, if a composition is disclosed and a number of modifications that can be made to a number of components of the composition are discussed, each and every combination and permutation that are possible are specifically contemplated unless specifically indicated to the contrary. Thus, if a class of components A, B, and C are disclosed as well as a class of components D, E, and F and an example of a composition A-D is disclosed, then even if each is not individually recited, each is individually and collectively contemplated. Thus, in this example, each of the combinations A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F are specifically contemplated and should be considered disclosed from disclosure of A, B, and C; D, E, and F; and the example combination A-D. Likewise, any subset or combination of these is also specifically contemplated and disclosed. Thus, for example, the sub-group of A-E, B-F, and C-E are specifically contemplated and should be considered disclosed from disclosure of A, B, and C; D, E, and F; and the example combination A-D. This concept applies to all aspects of this disclosure including, but not limited to, steps in methods of making and using the disclosed compositions. Thus, if there are a variety of additional steps that can be performed it is understood that each of these additional steps can be performed with any specific aspect or combination of aspects of the disclosed methods, and that each such combination is specifically contemplated and should be considered disclosed.

As a particular example of the subset concept, the range for any of the components of the glasses of the invention (including the range for a sum of the components) or the range for any property of those glasses, including, in particular, the range for the component or property set forth in a claim, can be narrowed (amended) at either the range's upper or lower end to any value for that component or property disclosed herein, whether the disclosure is a corresponding upper or lower end of another range for the component or property (e.g., a preferred range) or the amount of the component used in a particular example or a property exhibited by a particular example. With regard to narrowing claimed ranges based on examples, such narrowing applies irrespective of whether or not the remainder of the example is within the scope of the claim being narrowed.

Reference will now be made in detail to specific aspects of the disclosed materials, compounds, compositions, articles, and methods, examples of which are illustrated in the accompanying Examples and Figures.

Described herein are alkali-free glasses and methods for making the same that possess high strain points and, thus, good dimensional stability (i.e., low compaction). A high strain point glass can prevent panel distortion due to compaction/shrinkage during thermal processing subsequent to manufacturing of the glass.

It has been discovered that a glass with a strain point greater than 700° C. will minimize the dimensional changes (i.e., compaction) experienced by glass that is quickly cooled then reheated for a brief period of time. In one aspect, the glass compositions described herein have a strain point greater than or equal to 700° C. or greater than or equal to 710° C. In a further aspect, the glass compositions described herein have a strain point between 700° C. and 800° C., 700° C. and 775° C., 700° C. and 750° C., or 700° C. and 730° C. In a further aspect, the high strain point glass compositions described herein have a thermal compaction when subjected to a 600° C. heat treatment for 5 minutes that is less than 30 ppm, less than 25 ppm, less than 20 ppm, less than 15 ppm, or less than 10 ppm, with the lower compactions being preferred.

In one aspect, the glasses described herein have a strain point in excess of about 700° C. and experience less than 30 ppm compaction (i.e., dimensional change) after heat treatment for five minutes at 600° C. This temperature and duration were chosen to approximate a low temperature poly-silicon heat treatment cycle. FIG. 1 shows experimental data for a series of glasses with measured strain points along the x-axis, versus measured dimensional change after five minutes at 600° C.

In one aspect, described herein is an alkali-free glass comprising in mole percent on an oxide basis:

SiO₂ 64.0-72.0 Al₂O₃  9.0-16.0 B₂O₃ 1.0-5.0 MgO + La₂O₃ 1.0-7.5 CaO 2.0-7.5 SrO 0.0-4.5 BaO 1.0-7.0

wherein Σ(MgO+CaO+SrO+BaO+3La₂O₃)/(Al₂O₃)≧1.15, where Al₂O₃, MgO, CaO, SrO, BaO, and La₂O₃ represent the mole percents of the respective oxide components.

In a further aspect, described herein is an alkali-free glass comprising in mole percent on an oxide basis:

SiO₂ 64.0-72.0 B₂O₃ 1.0-5.0 Al₂O₃  9.0-16.0 MgO + La₂O₃ 1.0-7.5 CaO 2.0-7.5 SrO 0.0-4.5 BaO 1.0-7.0 wherein:

1.15 Σ(MgO+CaO+SrO+BaO+3La₂O₃)/(Al₂O₃)≦1.55, where Al₂O₃, MgO, CaO, SrO, BaO, and La₂O₃ represent the mole percents of the respective oxide components;

the glass has a strain point greater than or equal to 700° C.;

the glass has a temperature at 200 poise viscosity less than or equal to 1,665° C.; and

the glass has a viscosity at the liquidus temperature greater than or equal to 85,000 poise.

In another aspect, described herein is an alkali-free glass comprising in mole percent on an oxide basis:

SiO₂ 65.0-71.0 Al₂O₃  9.0-16.0 B₂O₃ 1.5-4.0 MgO + La₂O₃ 0.5-7.5 CaO 2.0-6.0 SrO 0.0-4.5 BaO 1.0-7.0 La₂O₃ >0.0 and less than or equal to 4.0 wherein Σ(MgO+CaO+SrO+BaO+3La₂O₃)/(Al₂O₃)≧1.15 (preferably, ≧1.2), where Al₂O₃, MgO, CaO, SrO, BaO, and La₂O₃ represent the mole percents of the respective oxide components.

In a further aspect, described herein is an alkali-free glass comprising in mole percent on an oxide basis:

SiO₂ 65.0-72.0 Al₂O₃ 10.0-15.0 B₂O₃ 1.0-4.0 MgO 2.0-7.5 CaO 3.0-6.0 SrO 0.0-4.5 BaO 1.0-6.0

wherein Σ(MgO+CaO+SrO+BaO)/(Al₂O₃)≧1.15, where Al₂O₃, MgO, CaO, SrO, and BaO represent the mole percents of the respective oxide components.

In an additional aspect, described herein is an alkali-free glass comprising SiO₂, Al₂O₃, B₂O₃, MgO, CaO, and at least one of SrO and BaO, wherein the glass' composition satisfies the relationship: [MgO]:[CaO]:[SrO+BaO]=1±0.15:1±0.15:1±0.15 (preferably, [MgO]:[CaO]:[SrO+BaO]=1±0.1:1±0.1:1±0.1),

where [MgO], [CaO], and [SrO+BaO] are the concentrations of the indicated components of the glass in mole percent on an oxide basis. Preferably, in connection with this aspect, the B₂O₃ concentration is less than or equal to 4.0 mole percent. As illustrated in the examples, it has been found that glasses that satisfy the above relationships have low liquidus temperatures (high liquidus viscosities) as is desired for downdraw processes, such as the fusion process. As discussed below, the SrO and BaO concentrations can be adjusted to optimize strain point, CTE, and density. Preferably, the BaO/SrO ratio in mole percent is equal to or greater than 2.0.

In the glass compositions described herein, SiO₂ serves as the basic glass former. In certain aspects, the concentration of SiO₂ can be greater than 64 mole percent in order to provide the glass with a density and chemical durability suitable for a flat panel display glass (e.g., an AMLCD glass), and a liquidus temperature (liquidus viscosity), which allows the glass to be formed by a downdraw process (e.g., a fusion process). In terms of an upper limit, in general, the SiO₂ concentration can be less than or equal to about 72.0 mole percent to allow batch materials to be melted using conventional, high volume, melting techniques, e.g., Joule melting in a refractory melter. As the concentration of SiO₂ increases, the 200 poise temperature (melting temperature) generally rises. In various applications, the SiO₂ concentration is adjusted so that the glass composition has a melting temperature less than or equal to 1,650° C. In one aspect, the SiO₂ concentration is between 66.0 and 71.0 mole percent or between 66.5 and 70.5 mole percent.

Al₂O₃ is another glass former used to make the glasses described herein. An Al₂O₃ concentration greater than or equal to 9.0 mole percent provides the glass with a low liquidus temperature and a corresponding high liquidus viscosity. The use of at least 9.0 mole percent Al₂O₃ also improves the glass' strain point and modulus. In order to achieve an Σ(MgO+CaO+SrO+BaO+3La₂O₃)/(Al₂O₃) ratio greater than or equal to 1.15 (see below), it is desirable to keep the Al₂O₃ concentration below 16.0 mole percent. In one aspect, the Al₂O₃ concentration is between 12.0 and 15.0 mole percent.

B₂O₃ is both a glass former and a flux that aids melting and lowers the melting temperature. To achieve these effects, the glass compositions described herein have B₂O₃ concentrations that are equal to or greater than 1.0 mole percent.

During the processing of displays, glass sheets are often held only at opposite edges, and therefore experience sagging in the unsupported central portion of the sheet. The amount of sag is a function of the geometry of the sheet, the density, and Young's modulus of the glass. The sheet geometry is dictated by the particular process employed, which is beyond the control of the glass manufacturer. For fixed density, an increase in Young's modulus is desirable since it reduces the amount of sag exhibited by large glass sheets during shipping, handling and thermal processing. Likewise, any increase in density should be accompanied by a proportionate increase in Young's modulus or it will result in increased sag. In one aspect, the glass has a density of less than or equal to 2.75 grams/cm³. In another aspect, to minimize the contribution of the glass itself to sag, it is desirable that the ratio of Young's modulus/density is greater than 30.0 GPa·cm³/g, greater than 30.5 GPa·cm³/g, greater than 31.2 GPa·cm³/g, or greater than 32.2 GPa·cm³/g, with higher ratios being preferred. While B₂O₃ reduces density when it replaces alkaline earth oxides, La₂O₃ or Al₂O₃, Young's modulus decreases more rapidly. Thus, it is desirable to keep B₂O₃ content as low as reasonably possible. B₂O₃ also tends to decrease strain point and, for this reason also, the B₂O₃ content of the glass is preferably kept as low as possible.

As discussed above with regard to SiO₂, glass durability is also very important for LCD applications. Durability can be controlled somewhat by elevated concentrations of alkaline earths and lanthanum oxides, and significantly reduced by elevated B₂O₃ content. As with strain point and Young's modulus, it is desirable to keep B₂O₃ content low. Thus, to achieve the above properties, in one aspect, the glasses described herein have B₂O₃ concentrations that are less than or equal to 5.0 mole percent, between 1.0 and 5.0 mole percent, between 1.0 and 4.0 mole percent, or between 2.0 and 4.0 mole percent.

The Al₂O₃ and B₂O₃ concentrations can be selected as a pair to increase strain point, increase modulus, improve durability, reduce density, and reduce the coefficient of thermal expansion (CTE), while maintaining the melting and forming properties of the glass.

For example, an increase in B₂O₃ and a corresponding decrease in Al₂O₃ can be helpful in obtaining a lower density and CTE, while an increase in Al₂O₃ and a corresponding decrease in B₂O₃ can be helpful in increasing strain point, modulus, and durability, provided that the increase in Al₂O₃ does not reduce the Σ(MgO+CaO+SrO+BaO)/(Al₂O₃) or Σ(MgO+CaO+SrO+BaO+3La₂O₃)/(Al₂O₃) ratio below about 1.15. For example, as known in the art, glasses for use in AMLCD applications have CTE's (0-300° C.) in the range of 28−42×10⁻⁷/° C., preferably, 30−40×10⁻⁷/° C., and most preferably, 32−38×10⁻⁷/° C. CTE's measured for other temperature ranges, e.g., 25-300° C. as in the examples presented below, can be transformed to the 0-300° C. range by adding an offset to the measured value. In the case of transforming CTE values measured for the 25-300° C. range to values for the 0-300° C. range, an offset of −0.8×10⁻⁷/° C. has been found to work successfully for AMLCD silica-based glasses. With regard to CTE, historically, lamp glasses have had low boron and high alkaline earth contents (leading to high alkaline earth to alumina ratios), but these glasses have purposely had CTE's above 42×10⁻⁷/° C. so that they would be compatible with molybdenum lead wires. Accordingly, the lamp glasses are not suitable for use in AMLCD applications.

In addition to the glass formers (SiO₂, Al₂O₃, and B₂O₃), the glasses described herein also include alkaline earth oxides. In one aspect, at least three alkaline earth oxides are part of the glass composition, e.g., MgO, CaO, and BaO, and, optionally, SrO. The alkaline earth oxides provide the glass with various properties important to melting, fining, forming, and ultimate use. Accordingly, to improve glass performance in these regards, in one aspect, the Σ(MgO+CaO+SrO+BaO)/(Al₂O₃) ratio is greater than or equal to 1.15, greater than or equal to 1.2, or greater than or equal to 1.25. In another aspect, the Σ(MgO+CaO+SrO+BaO)/(Al₂O₃) ratio is less than or equal to 1.55 or less than or equal to 1.50.

The concentrations of MgO, La₂O₃, or combinations thereof, in the glass and the Σ(MgO+CaO+SrO+BaO+3La₂O₃)/(Al₂O₃) ratio of the glass, can influence glass performance, particularly meltability and fining. Accordingly, to improve glass performance in these regards, in one aspect, the Σ(MgO+CaO+SrO+BaO+3La₂O₃)/(Al₂O₃) ratio is greater than or equal to 1.15, greater than or equal to 1.20, or greater than or equal to 1.25. In another aspect, the Σ(MgO+CaO+SrO+BaO+3La₂O₃)/(Al₂O₃) ratio is greater than or equal to 1.15 and less than or equal to 1.55, or greater than or equal to 1.25 and less than or equal to 1.45.

For certain embodiments of this invention, MgO and La₂O₃ are treated as what is in effect a single compositional component. This is because their impact upon viscoelastic properties, liquidus temperatures and liquidus phase relationships are qualitatively very similar. The other alkaline earth oxides form feldspar minerals, notably anorthite (CaAl₂Si₂O₈) and celsian (BaAl₂Si₂O₈) and strontium-bearing solid solutions of same. Neither MgO nor La₂O₃ participate in these crystals to a significant degree. Therefore, when a feldspar crystal is already the liquidus phase, a superaddition of MgO or La₂O₃ actual serves to stabilize the liquid relative to the crystal and thus lower the liquidus temperature. At the same time, the viscosity curve typically becomes steeper, reducing melting temperatures while having little or no impact on low-temperature viscosities. In this sense, the addition of small amounts of MgO and/or La₂O₃ benefits melting by reducing melting temperatures, benefits forming by reducing liquidus temperatures and increasing liquidus viscosity, while preserving high strain point and, thus, low compaction.

The impact of MgO and La₂O₃ on these properties is similar, but their impact on other key glass properties is very different. La₂O₃ greatly increases density and mildly increases CTE relative to MgO. While Young's modulus typically increases when either is added to an aluminosilicate glass of the invention, the density increases so quickly with La₂O₃ content that the specific modulus (Young's modulus divided by density) decreases. It is desirable to have a specific modulus of at least 28 MPa·m³/kg, a typical value for AMLCD substrates in order to avoid excessive sagging of the sheet during thermal processing. Young's modulus for the glasses of this invention range from about 77.6 to about 83 GPa, and thus when density is greater than about 2.75 g/cc the specific modulus will fall below the desired level. For this reason, it is necessary to constrain La₂O₃ to be no higher than necessary to produce the desired impact on viscoelastic properties. While MgO does not have this impact, at high concentrations it finds high solubility in the barium aluminosilicate celsian, and thus for liquidus purposes must be kept at or below a level comparable to that for La₂O₃.

By increasing the sum of MgO+La₂O₃, the liquidus temperature can rise and the liquidus viscosity can fall to a level such that the use of a high viscosity forming process (e.g., a fusion process) is compromised. Therefore, the amount of MgO and La₂O₃ can be adjusted accordingly to obtain the desired properties for glass formation. In terms of concentrations, when both are present, the combined concentration of MgO+La₂O₃ should be between 1.0 and 7.5 mole percent in order to achieve the various benefits described above. In another aspect, the MgO concentration is between 2.0 and 6.0 mole percent or between 3.0 and 6.0 mole percent, especially when MgO is used in the absence of La₂O₃. In a further aspect, the La₂O₃ concentration is preferably kept less than or equal to about 3.0 mole percent so as not to elevate the density of the glass.

Calcium oxide present in the glass composition can produce low liquidus temperatures (high liquidus viscosities), high strain points and moduli, and CTE's in the most desired ranges for flat panel applications, specifically, AMLCD applications. It also contributes favorably to chemical durability, and compared to other alkaline earth oxides, it is relatively inexpensive as a batch material. However, at high concentrations, CaO increases the density and CTE. Furthermore, at sufficiently low SiO₂ concentrations, CaO may stabilize anorthite, thus decreasing liquidus viscosity. Accordingly, in one aspect, the CaO concentration can be greater than or equal to 2.0 mole percent. In another aspect, the CaO concentration of the glass composition is less than or equal to 7.5 mole percent or is between 3.0 and 7.5 mole percent.

The remaining alkaline earth oxides SrO and BaO can both contribute to low liquidus temperatures (high liquidus viscosities) and, thus, the glasses described herein will typically contain at least one of these oxides. However, the selection and concentration of these oxides are selected in order to avoid an increase in CTE and density and a decrease in modulus and strain point. The relative proportions of SrO and BaO can be balanced so as to obtain a suitable combination of physical properties and liquidus viscosity such that the glass can be formed by a downdraw process.

To summarize the effects/roles of the central components of the glasses of the invention, SiO₂ is the basic glass former. Al₂O₃ and B₂O₃ are also glass formers and can be selected as a pair with, for example, an increase in B₂O₃ and a corresponding decrease in Al₂O₃ being used to obtain a lower density and CTE, while an increase in Al₂O₃ and a corresponding decrease in B₂O₃ being used in increasing strain point, modulus, and durability, provided that the increase in Al₂O₃ does not reduce the RO/(Al₂O₃) or (RO+3La₂O₃)/(Al₂O₃) ratio below about 1.15, where RO=Σ(MgO+CaO+SrO+BaO). If the ratio goes too low, meltability is compromised, i.e., the melting temperature becomes too high. B₂O₃ can be used to bring the melting temperature down, but high levels of B₂O₃ compromise strain point.

In addition to meltability and strain point considerations, for AMLCD applications, the CTE of the glass should be compatible with that of silicon. To achieve such CTE values, the glasses of the invention control the RO content of the glass (or the RO+3La₂O₃ content for glasses that include La₂O₃). For a given Al₂O₃ content, controlling the RO content corresponds to controlling the RO/Al₂O₃ ratio (or the (RO+3La₂O₃)/Al₂O₃ ratio for glasses that include La₂O₃). In practice, glasses having suitable CTE's are produced if the RO/Al₂O₃ ratio (or the (RO+3La₂O₃)/Al₂O₃ ratio) is below about 1.55.

On top of these considerations, the glasses are preferably formable by a downdraw process, e.g., a fusion process, which means that the glass' liquidus viscosity needs to be relatively high. Individual alkaline earths play an important role in this regard since they can destabilize the crystalline phases that would otherwise form. BaO and SrO are particularly effective in controlling the liquidus viscosity and are included in the glasses of the invention for at least this purpose. As illustrated in the examples presented below, various combinations of the alkaline earths will produce glasses having high liquidus viscosities, with the total of the alkaline earths (and La₂O₃ when used) satisfying the RO/Al₂O₃ ratio (or the (RO+3La₂O₃)/Al₂O₃ ratio) constraints needed to achieve low melting temperatures, high strain points, and suitable CTE's.

In addition to the above components, the glass compositions described herein can include various other oxides to adjust various physical, melting, fining, and forming attributes of the glasses. Examples of such other oxides include, but are not limited to, TiO₂, MnO, Fe₂O₃, ZnO, Nb₂O₅, MoO₃, Ta₂O₅, WO₃, Y₂O₃, and CeO₂. In one aspect, the amount of each of these oxides can be less than or equal to 2.0 mole percent, and their total combined concentration can be less than or equal to 4.0 mole percent. The glass compositions described herein can also include various contaminants associated with batch materials and/or introduced into the glass by the melting, fining, and/or forming equipment used to produce the glass, particularly Fe₂O₃ and ZrO₂. The glasses can also contain SnO₂ either as a result of Joule melting using tin-oxide electrodes and/or through the batching of tin containing materials, e.g., SnO₂, SnO, SnCO₃, SnC₂O₄, etc.

The glass compositions are generally alkali free; however, the glasses can contain some alkali contaminants. In the case of AMLCD applications, it is desirable to keep the alkali levels below 0.1 mole percent to avoid having a negative impact on thin film transistor (TFT) performance through diffusion of alkali ions from the glass into the silicon of the TFT. As used herein, an “alkali-free glass” is a glass having a total alkali concentration which is less than or equal to 0.1 mole percent, where the total alkali concentration is the sum of the Na₂O, K₂O, and Li₂O concentrations. In one aspect, the total alkali concentration is less than or equal to 0.07 mole percent.

As discussed above, Σ(MgO+CaO+SrO+BaO)/(Al₂O₃) and Σ(MgO+CaO+SrO+BaO+3La₂O₃)/(Al₂O₃) ratios greater than or equal to 1.15 improve fining, i.e., the removal of gaseous inclusions from the melted batch materials. This improvement allows for the use of more environmentally friendly fining packages. For example, on an oxide basis, the glass compositions described herein can have one or more or all of the following compositional characteristics:

an As₂O₃ concentration of at most 0.05 mole percent;

an Sb₂O₃ concentration of at most 0.05 mole percent;

a SnO₂ concentration of at most 0.2 mole percent.

As₂O₃ is an effective high temperature fining agent for AMLCD glasses, and in some aspects described herein, As₂O₃ is used for fining because of its superior fining properties. However, As₂O₃ is poisonous and requires special handling during the glass manufacturing process. Accordingly, in certain aspects, fining is performed without the use of substantial amounts of As₂O₃, i.e., the finished glass has at most 0.05 mole percent As₂O₃. In one aspect, no As₂O₃ is purposely used in the fining of the glass. In such cases, the finished glass will typically have at most 0.005 mole percent As₂O₃ as a result of contaminants present in the batch materials and/or the equipment used to melt the batch materials.

Although not as toxic as As₂O₃, Sb₂O₃ is also poisonous and requires special handling. In addition, Sb₂O₃ raises the density, raises the CTE, and lowers the strain point in comparison to glasses that use As₂O₃ or SnO₂ as a fining agent. Accordingly, in certain aspects, fining is performed without the use of substantial amounts of Sb₂O₃, i.e., the finished glass has at most 0.05 mole percent Sb₂O₃. In another aspect, no Sb₂O₃ is purposely used in the fining of the glass. In such cases, the finished glass will typically have at most 0.005 mole percent Sb₂O₃ as a result of contaminants present in the batch materials and/or the equipment used to melt the batch materials.

Compared to As₂O₃ and Sb₂O₃ fining, tin fining (i.e., SnO₂ fining) is less effective, but SnO₂ is a ubiquitous material that has no known hazardous properties. Also, for many years, SnO₂ has been a component of AMLCD glasses through the use of tin oxide electrodes in the Joule melting of the batch materials for such glasses. The presence of SnO₂ in AMLCD glasses has not resulted in any known adverse effects in the use of these glasses in the manufacture of liquid crystal displays. However, high concentrations of SnO₂ are not preferred as this can result in the formation of crystalline defects in AMLCD glasses. In one aspect, the concentration of SnO₂ in the finished glass is less than or equal to 0.2 mole percent.

Tin fining can be used alone or in combination with other fining techniques if desired. For example, tin fining can be combined with halide fining, e.g., bromine fining. Other possible combinations include, but are not limited to, tin fining plus sulfate, sulfide, cerium oxide, mechanical bubbling, and/or vacuum fining. It is contemplated that these other fining techniques can be used alone. In certain aspects, maintaining the Σ(MgO+CaO+SrO+BaO+3La₂O₃)/(Al₂O₃) ratio and individual alkaline earth and La₂O₃ concentrations within the ranges discussed above makes the fining process easier to perform and more effective.

The glasses described herein can be manufactured using various techniques known in the art. In one aspect, the glasses are made using a downdraw process such as, for example, a fusion downdraw process. In one aspect, described herein is a method for producing an alkali-free glass sheet by a downdraw process comprising selecting, melting, and fining batch materials so that the glass making up the sheets comprises SiO₂, Al₂O₃, B₂O₃, MgO, CaO and BaO, and, on an oxide basis, comprises:

a Σ(MgO+CaO+SrO+BaO)/(Al₂O₃) ratio greater than or equal to 1.15;

(ii) a MgO content greater than or equal to 2.0 mole percent;

a CaO content greater than or equal to 3.0 mole percent; and

a BaO content greater than or equal to 1.0 mole percent,

wherein:

the fining is performed without the use of substantial amounts of arsenic (and, optionally, without the use of substantial amounts of antimony); and

a population of 50 sequential glass sheets produced by the downdraw process from the melted and fined batch materials has an average gaseous inclusion level of less than 0.10 gaseous inclusions/cubic centimeter, where each sheet in the population has a volume of at least 500 cubic centimeters.

U.S. Pat. No. 5,785,726 (Dorfeld et al.), U.S. Pat. No. 6,128,924 (Bange et al.), U.S. Pat. No. 5,824,127 (Bange et al.), and co-pending patent application Ser. No. 11/116,669 disclose processes for manufacturing arsenic free glasses.

In one aspect, the population of 50 sequential glass sheets produced by the downdraw process from the melted and fined batch materials has an average gaseous inclusion level of less than 0.05 gaseous inclusions/cubic centimeter, where each sheet in the population has a volume of at least 500 cubic centimeters.

The downdraw sheet drawing processes and, in particular, the fusion process described in U.S. Pat. Nos. 3,338,696 and 3,682,609 both to Dockerty, which are incorporated by reference, can be used herein. Compared to other forming processes, such as the float process, the fusion process is preferred for several reasons. First, glass substrates made from the fusion process do not require polishing. Current glass substrate polishing is capable of producing glass substrates having an average surface roughness greater than about 0.5 nm (Ra), as measured by atomic force microscopy. The glass substrates produced by the fusion process have an average surface roughness as measured by atomic force microscopy of less than 0.5 nm. The substrates also have an average internal stress as measured by optical retardation which is less than or equal to 150 psi.

To be formed by a downdraw process, it is desirable that the glass compositions described herein have a liquidus viscosity greater than or equal to 85,000 poises, greater than or equal to 100,000 poises, or greater than or equal to 150,000 poises, higher liquidus viscosities being preferable.

The glass compositions described herein can be used to make various glass articles. For example, the glass compositions described herein can be used to make substrates for liquid crystal displays such as, for example, AMLCDs. In one aspect, to be suitable for use in flat panel display applications such as, for example, AMLCDs, the glasses described herein have a value for (Young's modulus)/density>30.5 GPa·cm³/g, a weight loss which is less than or equal to 0.8 milligrams/cm² when a polished sample is exposed to a 5% HCl solution for 24 hours at 95° C., and a weight loss of less than 1.5 milligrams/cm² when exposed to a solution of 1 volume of 50 wt. % HF and 10 volumes 40 wt. % NH₄F at 30° C. for 5 minutes.

EXAMPLES

The following examples are set forth below to illustrate the methods and results according to the disclosed subject matter. These examples are not intended to be inclusive of all aspects of the subject matter disclosed herein, but rather to illustrate representative methods and results. These examples are not intended to exclude equivalents and variations of the present invention which are apparent to one skilled in the art.

Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.) but some errors and deviations should be accounted for. Unless indicated otherwise, temperature is in ° C. or is at ambient temperature, and pressure is at or near atmospheric. The compositions themselves are given in mole percent on an oxide basis and have been normalized to 100%. There are numerous variations and combinations of reaction conditions, e.g., component concentrations, temperatures, pressures and other reaction ranges and conditions that can be used to optimize the product purity and yield obtained from the described process. Only reasonable and routine experimentation will be required to optimize such process conditions.

Example 1 Preparation of a Test Sample

Test glass samples are made by melting appropriate batch materials in Pt crucibles at 1,600-1,650° C. for 6 or more hours, and pouring onto a steel sheet, followed by conventional annealing prior to cutting and polishing for testing. The resulting patty of glass is processed to yield rectangular or square glass samples roughly 3″×7″×2 mm thick or 4″×4″×2 mm thick. The glass rectangles or squares are heated to a temperature corresponding to a viscosity of 10¹¹ poise and held for four hours, followed by quick cooling to room temperature. This heat treatment is believed to give the best possible approximation to the thermal history of fusion drawn sheet. The samples are then polished on their flat surfaces, marked with sets of several fiducial marks near their edges (and perpendicular to the long axis of the sample in the case of rectangular samples). Rectangular samples are cut in half lengthwise, leaving one reference portion, and another portion that undergoes heat treatment(s). The reference piece and the heat-treated piece are examined together under a microscope, and dimensional changes are recorded. Dimensions of square samples are precisely measured before heat treatment using a Mitutoyo Quick Vision QV202 Pro instrument, followed by heat treatment(s) at appropriate times and temperatures, and re-measurement of sample dimensions. Because the automated optical instrument makes several tens of repeat measurements on each sample, statistical methods can be used to determine dimensional changes as low as 1 micron, corresponding to less than a 5 to 10 ppm dimensional change for the sample sizes used. Repeated heat treatments and measurements can be used to determine the dimensional relaxation behavior of a glass at a given temperature as a function of time.

FIG. 1 shows the results of compaction testing performed on a series of commercial and laboratory glasses to investigate the effects of strain point on compaction. As can be seen in this figure, the change in compaction with strain point is a non-linear phenomenon, with the largest improvement occurring over the 20° C. range between 660° C. and 680° C. In this regard, it should be noted that 660° C. is a typical strain point value for AMLCD glasses currently on the market. By increasing the strain point by just 20° C. to 680° C., the compaction drops from above 70 ppm to less than 30 ppm, i.e., an improvement of more than 50%. For some poly-Si processes, this improvement may be sufficient. For other processes, further improvements may be required. As illustrated in FIG. 1, increases in the strain point from 660° C. by 50-100° C. or more, achieve compaction levels of 20 ppm and below. These levels are suitable for poly-Si processes currently in use or expected to be used in the coming years.

FIG. 2 shows the effects of repeated heat treatments on glasses having different strain points. Repeated heat treatments more accurately mimic the poly-Si manufacturing process than the single heat treatment used to generate the data of FIG. 1. For FIG. 2, each of three glasses, i.e., Glass A which corresponds to Example 68 of Table 1, Glass B which corresponds to Example 65 of Table 1, and Glass C which is Corning Eagle 2000F glass, was inserted in a furnace at 600° C. and held at temperature for increasing periods of time as the experiment continued. For the first heat treatment, the period was 5 minutes, for the second period it was an additional five minutes (for a total time of 10 minutes), and so forth as shown in Table 2, with the last four periods being for 60 minutes each. After each heat treatment, the glass sample was removed from the furnace and placed between two fans to achieve rapid cooling. In this way, the glass samples were basically subjected to step changes in their temperatures.

As can be seen in FIG. 2, for all three samples, the compaction per test period decreases with increasing time since the glass structure has relaxed based on its prior exposures to the 600° C. treatments. However, the glasses with higher strain points, i.e., Glasses A and B of the invention, exhibited markedly lower levels of compaction than Glass C which had a strain point characteristic of currently available AMLCD glasses. The data plotted in FIG. 2 is set forth in Table 2.

In addition to low compaction, the glass must satisfy rigorous forming requirements to be applicable to fusion draw or related processes. Devitrification is defined as the formation of a crystalline phase from an initially homogeneous glass. The maximum temperature at which crystals coexist with glass is defined as the liquidus temperature. As described below in connection with the testing of the glasses of Table 1, liquidus temperature is measured by loading a crushed glass sample into a platinum boat, then heating for 24 hours in a tube furnace with a gradient of 10° C. or less per cm. The viscosity of the glass at the liquidus temperature is referred to as the liquidus viscosity. Precision sheet glass forming processes generally require comparatively high liquidus viscosities, for example, greater than 40,000 poise, preferably, greater than 85,000 poise.

The glass must also satisfy rigorous melting requirements for production purposes. The temperature at which glass batch constituents melt in a economically reasonable amount of time, and the temperature at which trapped bubbles of air can rise out of the glass in a reasonable amount of time, typically corresponds to a viscosity of about 200 poises. Limitations in durable refractory or precious metal containers at high temperatures place an upper practical limit for 200 poises temperature of about 1,680° C. It is possible that changes in batch materials from those conventionally used would allow more viscous glasses to be melted at proportionately higher viscosities, but such materials invariably add formidable costs, and transporting glass through a melting and conditioning system at high viscosity presents significant technical challenges. Numerous glass compositions with their physical properties are presented in Table 1.

The glass properties set forth in Table 1 were determined in accordance with techniques conventional in the glass art. Thus, the linear coefficient of thermal expansion (CTE) over the temperature range 25-300° C. is expressed in terms of ×10⁻⁷PC and the strain point is expressed in terms of ° C. These were determined from fiber elongation techniques (ASTM references E228-85 and C336, respectively).

The density in terms of grams/cm³ was measured via the Archimedes method (ASTM C693).

The melting temperature in terms of ° C. (defined as the temperature at which the glass melt demonstrates a viscosity of 200 poises) was calculated employing a Fulcher equation fit to high temperature viscosity data measured via rotating cylinders viscometry (ASTM C965-81).

The liquidus temperature of the glass in terms of ° C. was measured using the standard gradient boat liquidus method of ASTM C829-81. This involves placing crushed glass particles in a platinum boat, placing the boat in a furnace having a region of gradient temperatures, heating the boat in an appropriate temperature region for 24 hours, and determining by means of microscopic examination the highest temperature at which crystals appear in the interior of the glass. More particularly, the glass sample is removed from the Pt boat in one piece, and examined using polarized light microscopy to identify the location and nature of crystals which have formed against the Pt and air interfaces, and in the interior of the sample. Because the gradient of the furnace is very well known, temperature vs location can be well estimated, within 5-10° C. The temperature at which crystals are observed in the internal portion of the sample is taken to represent the liquidus of the glass (for the corresponding test period). Testing is sometimes carried out at longer times (e.g. 72 hours), in order to observe slower growing phases. The crystalline phase for the various glasses of Table 1 are described by the following abbreviations: anor—anorthite, a calcium aluminosilicate mineral; cris—cristobalite (SiO₂); cels—mixed alkaline earth celsian; Sr/Al sil—a strontium aluminosilicate phase; SrSi—a strontium silicate phase. The liquidus viscosity in poises was determined from the liquidus temperature and the coefficients of the Fulcher equation.

Young's modulus values in terms of Gpa were determined using a resonant ultrasonic spectroscopy technique of the general type set forth in ASTM E1875-00e1.

As can be seen in Table 1, Examples 1-88 have densities, CTE's, strain points, and Young's modulus values that make the glasses suitable for use in display applications, such as AMLCD applications. Although not shown in Table 1, the glasses also have chemical durabilities suitable for these applications. In particular, Examples 68, 69, 70, and 71 were each found to have weight loss values when immersed in 10 wt. % HF for 20 minutes at room temperature of between 6.7 and 7.5 milligrams/cm². For comparison, commercial AMLCD glasses show weight losses in the range of 5-8 milligrams/cm² when tested in this manner. The glasses of all the examples can be formed using downdraw techniques, such as the fusion technique. Thus, they have liquidus temperatures less than or equal to 1250° C. and liquidus viscosities equal to or greater than 85,000 poises, and in most cases, equal to or greater than 150,000 poises.

Glasses having the composition and properties shown in Examples 71 and 79 are currently regarded as representing the most preferred embodiments of the invention, that is, as providing the best combination of properties for the purposes of the invention at this time.

Throughout this application, various publications are referenced. The disclosures of these publications in their entireties are hereby incorporated by reference into this application in order to more fully describe the compounds, compositions and methods described herein.

Various modifications and variations can be made to the materials, methods, and articles described herein. Other aspects of the materials, methods, and articles described herein will be apparent from consideration of the specification and practice of the materials, methods, and articles disclosed herein. It is intended that the specification and examples be considered as exemplary.

TABLE 1 Mol % min max 1 2 3 4 SiO₂ 66.58 70.69 67.63 66.58 68.76 67.61 Al₂O₃ 11.75 13.51 12.15 12.14 11.76 11.89 B₂O₃ 1.25 4.96 3.98 3.99 4.96 3.94 MgO 0.84 7.48 5.28 5.66 3.02 5.42 CaO 2.99 5.89 5.28 5.66 5.57 5.42 SrO 0.00 4.29 0.00 1.96 0.68 1.88 BaO 1.30 5.55 5.28 3.77 5.00 3.60 La₂O₃ 0.00 3.01 0.00 0.00 0.00 0.00 As₂O₃ 0.00 0.40 0.40 0.25 0.25 0.25 Sb₂O₃ 0.00 0.49 0.00 0.00 0.00 0.00 ZrO₂ 0.00 0.02 0.00 0.00 0.00 0.00 SnO₂ 0.00 0.08 0.00 0.00 0.00 0.00 MgO + La₂O₃ 2.35 7.48 5.28 5.66 3.02 5.42 Sum(RO + La2/3O)* 14.27 18.39 15.84 17.05 14.27 16.32 Sum(RO + La2/3O)/Al₂O₃ 1.15 1.41 1.30 1.40 1.21 1.37 Strain Point (° C.) 695 739 — 706 715 702 CTE (×10−7/° C.) 35.8 39.6 — 39 37.6 38.5 density 2.571 2.842 2.631 2.628 2.610 2.619 Young's modulus (Gpa) 77.6 82.6 — — 78.1 — specific modulus 29.1 31.5 — — 29.9 — 200 poise T (° C.) 1585 1672 — 1585 1665 1605 Liquidus T (° C.) 1110 1250 1110 1115 1120 1125 Liquidus phase — — cels cris anor anor Liquidus Viscosity 1.09E+05 1.08E+06 — 4.59E+05 1.08E+06 4.48E+05 Mol % 5 6 7 8 9 10 SiO₂ 67.43 68.90 67.95 67.20 69.81 69.59 Al₂O₃ 11.75 12.02 12.03 11.89 11.89 11.99 B₂O₃ 3.93 3.82 3.94 3.99 4.00 3.94 MgO 5.48 4.15 5.23 5.54 2.70 3.05 CaO 5.48 5.78 5.23 5.54 5.81 5.78 SrO 1.89 1.04 0.00 1.92 0.89 0.93 BaO 3.64 4.29 5.23 3.68 4.90 4.72 La₂O₃ 0.00 0.00 0.00 0.00 0.00 0.00 As₂O₃ 0.40 0.00 0.39 0.25 0.00 0.00 Sb₂O₃ 0.00 0.00 0.00 0.00 0.00 0.00 ZrO₂ 0.00 0.00 0.00 0.00 0.00 0.00 SnO₂ 0.00 0.00 0.00 0.00 0.00 0.00 MgO + La₂O₃ 5.48 4.15 5.23 5.54 2.70 3.05 Sum(RO + La2/3O)* 16.49 15.26 15.69 16.68 14.30 14.48 Sum(RO + La2/3O)/Al₂O₃ 1.40 1.27 1.30 1.40 1.20 1.21 Strain Point (° C.) 703 705 — 706 701 705 CTE (×10−7/° C.) 37.6 37.5 — 39.4 — 37.2 density 2.611 2.598 2.628 2.616 2.593 2.593 Young's modulus (Gpa) 80 — — — — — specific modulus 30.6 — — — — — 200 poise T (° C.) 1618 1642 — 1601 — 1664 Liquidus T (° C.) 1125 1130 1130 1130 1135 1135 Liquidus phase anor anor cels anor anor + cris anor Liquidus Viscosity 4.78E+05 5.78E+05 — 3.43E+05 — 6.64E+05 Mol % 11 12 13 14 15 16 SiO₂ 70.69 69.83 69.76 69.36 68.01 67.93 Al₂O₃ 12.48 11.89 11.95 11.96 12.49 12.37 B₂O₃ 4.72 3.97 4.00 3.90 3.94 3.94 MgO 0.84 2.70 2.78 3.90 5.09 5.16 CaO 4.69 5.80 5.77 5.70 5.09 5.16 SrO 1.36 0.89 0.89 0.88 1.76 1.79 BaO 3.71 4.92 4.85 4.30 3.38 3.41 La₂O₃ 1.51 0.00 0.00 0.00 0.00 0.00 As₂O₃ 0.00 0.00 0.00 0.00 0.25 0.25 Sb₂O₃ 0.00 0.00 0.00 0.00 0.00 0.00 ZrO₂ 0.00 0.00 0.00 0.00 0.00 0.00 SnO₂ 0.00 0.00 0.00 0.00 0.00 0.00 MgO + La₂O₃ 2.35 2.70 2.78 3.90 5.09 5.16 Sum(RO + La2/3O)* 15.13 14.31 14.29 14.78 15.32 15.52 Sum(RO + La2/3O)/Al₂O₃ 1.21 1.20 1.20 1.24 1.23 1.25 Strain Point (° C.) 719 703 704 698 708 707 CTE (×10−7/° C.) 36.7 37.1 — 37.3 37 37.6 density 2.673 2.592 — 2.595 2.597 2.600 Young's modulus (Gpa) 77.7 77.63 — 79.01 — — specific modulus 29.1 29.9 — 30.5 — — 200 poise T (° C.) 1648.19 1672 1672 1651 1624 1620 Liquidus T (° C.) 1140 1140 1140 1140 1140 1140 Liquidus phase cris anor anor anor anor anor Liquidus Viscosity 7.01E+05 7.11E+05 6.53E+05 4.81E+05 4.19E+05 3.78E+05 Mol % 17 18 19 20 21 22 SiO₂ 67.85 68.26 66.89 70.25 67.69 69.80 Al₂O₃ 12.25 11.91 12.01 12.99 12.01 13.51 B₂O₃ 3.94 3.91 3.99 4.52 3.94 4.32 MgO 5.22 5.18 5.60 0.88 5.36 0.90 CaO 5.22 5.18 5.60 4.37 5.36 4.06 SrO 1.81 0.00 1.94 1.26 1.85 1.16 BaO 3.47 5.18 3.73 3.47 3.55 3.24 La₂O₃ 0.00 0.00 0.00 2.26 0.00 3.01 As₂O₃ 0.25 0.39 0.25 0.00 0.25 0.00 Sb₂O₃ 0.00 0.00 0.00 0.00 0.00 0.00 ZrO₂ 0.00 0.00 0.00 0.00 0.00 0.00 SnO₂ 0.00 0.00 0.00 0.00 0.00 0.00 MgO + La₂O₃ 5.22 5.18 5.60 3.14 5.36 3.91 Sum(RO + La2/3O)* 15.72 15.54 16.87 16.76 16.12 18.39 Sum(RO + La2/3O)/Al₂O₃ 1.28 1.30 1.40 1.29 1.34 1.36 Strain Point (° C.) 703 — 703 725 705 729 CTE (×10−7/° C.) 37.8 — 39.6 37.2 38.7 39.3 density 2.605 2.622 2.623 2.723 2.598 2.842 Young's modulus (Gpa) — — — 79.57 — 82.6 specific modulus — — — 29.2 — 29.1 200 poise T (° C.) 1609 — 1606 1620 1600 1586 Liquidus T (° C.) 1140 1140 1140 1145 1145 1150 Liquidus phase anor cels anor cris cris cris Liquidus Viscosity 3.63E+05 — 2.78E+05 4.78E+05 2.56E+05 3.02E+05 Mol % 23 24 25 26 27 28 SiO₂ 68.29 67.77 68.28 68.38 68.38 68.20 Al₂O₃ 12.11 12.13 12.07 12.04 12.04 11.89 B₂O₃ 3.68 3.94 2.69 2.99 2.99 2.99 MgO 4.46 5.29 5.30 5.45 5.45 5.54 CaO 5.82 5.29 5.78 5.45 5.45 5.54 SrO 1.44 1.83 1.92 1.09 0.00 1.92 BaO 4.20 3.51 3.64 4.36 5.45 3.68 La₂O₃ 0.00 0.00 0.00 0.00 0.00 0.00 As₂O₃ 0.00 0.25 0.26 0.25 0.25 0.25 Sb₂O₃ 0.00 0.00 0.00 0.00 0.00 0.00 ZrO₂ 0.00 0.00 0.02 0.00 0.00 0.00 SnO₂ 0.00 0.00 0.03 0.00 0.00 0.00 MgO + La₂O₃ 4.46 5.29 5.30 5.45 5.45 5.54 Sum(RO + La2/3O)* 15.92 15.92 16.64 16.35 16.35 16.68 Sum(RO + La2/3O)/Al₂O₃ 1.31 1.31 1.38 1.36 1.36 1.40 Strain Point (° C.) 698 705 — — — 715 CTE (×10−7/° C.) 37.9 37.3 — — — 39.2 density 2.602 2.607 — 2.627 2.655 2.631 Young's modulus (Gpa) 79.98 — — — — — specific modulus 30.7 — — — — — 200 poise T (° C.) 1635 1611 1611 — — 1614 Liquidus T (° C.) 1150 1150 1150 1150 1150 1150 Liquidus phase anor anor cris cris + cels cels anor Liquidus Viscosity 3.39E+05 2.56E+05 2.27E+05 — — 2.91E+05 Mol % 29 30 31 32 33 34 SiO₂ 68.38 68.38 67.74 68.38 69.53 68.53 Al₂O₃ 12.04 12.04 12.08 12.04 11.95 12.15 B₂O₃ 2.99 2.99 2.99 2.99 3.93 3.69 MgO 5.45 5.45 5.63 5.68 3.12 5.08 CaO 5.45 5.45 5.63 4.98 5.46 5.08 SrO 1.56 1.82 1.95 2.13 2.37 0.00 BaO 3.89 3.63 3.74 3.55 3.39 5.08 La₂O₃ 0.00 0.00 0.00 0.00 0.00 0.00 As₂O₃ 0.25 0.25 0.25 0.25 0.25 0.40 Sb₂O₃ 0.00 0.00 0.00 0.00 0.00 0.00 ZrO₂ 0.00 0.00 0.00 0.00 0.00 0.00 SnO₂ 0.00 0.00 0.00 0.00 0.00 0.00 MgO + La₂O₃ 5.45 5.45 5.63 5.68 3.12 5.08 Sum(RO + La2/3O)* 16.35 16.35 16.95 16.34 14.34 15.24 Sum(RO + La2/3O)/Al₂O₃ 1.36 1.36 1.40 1.36 1.20 1.25 Strain Point (° C.) — — 715 — 717 703 CTE (×10−7/° C.) — — 39.2 — 38 38 density 2.620 2.628 2.636 2.617 2.595 2.620 Young's modulus (Gpa) — — — — — — specific modulus — — — — — — 200 poise T (° C.) — — 1609 — 1664 — Liquidus T (° C.) 1155 1155 1155 1155 1160 1160 Liquidus phase cels anor anor anor anor cels Liquidus Viscosity — — 2.37E+05 — 3.68E+05 — Mol % 35 36 37 38 39 40 SiO₂ 68.70 68.38 67.53 67.53 67.86 68.38 Al₂O₃ 12.20 12.04 11.77 11.77 12.23 12.04 B₂O₃ 2.89 2.99 3.89 3.89 2.73 2.99 MgO 5.16 5.45 5.49 5.99 5.98 6.02 CaO 5.83 5.45 5.49 4.49 5.24 4.29 SrO 1.46 1.82 3.09 1.90 1.95 2.58 BaO 3.76 3.63 2.49 4.19 3.69 3.44 La₂O₃ 0.00 0.00 0.00 0.00 0.00 0.00 As₂O₃ 0.00 0.25 0.25 0.25 0.26 0.25 Sb₂O₃ 0.00 0.00 0.00 0.00 0.00 0.00 ZrO₂ 0.00 0.00 0.00 0.00 0.02 0.00 SnO₂ 0.00 0.00 0.00 0.00 0.03 0.00 MgO + La₂O₃ 5.16 5.45 5.49 5.99 5.98 6.02 Sum(RO + La2/3O)* 16.21 16.35 16.56 16.57 16.86 16.33 Sum(RO + La2/3O)/Al₂O₃ 1.33 1.36 1.41 1.41 1.38 1.36 Strain Point (° C.) 712 — 707 — — — CTE (×10−7/° C.) 37.9 — 38.7 — — — density 2.607 2.619 2.608 2.630 2.618 2.624 Young's modulus (Gpa) 81.15 — — — — — specific modulus 31.1 — — — — — 200 poise T (° C.) 1629 — 1601 — — — Liquidus T (° C.) 1160 1160 1160 1160 1160 1160 Liquidus phase anor cris anor cels anor cris + anor Liquidus Viscosity 2.68E+05 — 1.66E+05 — — — Mol % 41 42 43 44 45 46 SiO₂ 67.53 68.38 67.73 67.27 68.38 68.34 Al₂O₃ 11.77 12.04 12.23 12.27 12.04 12.22 B₂O₃ 3.89 2.99 3.19 2.99 2.99 2.60 MgO 6.48 4.67 5.27 5.72 4.99 5.37 CaO 5.49 5.84 5.89 5.72 5.68 5.85 SrO 0.90 1.17 2.06 1.98 2.12 1.95 BaO 3.69 4.67 3.63 3.81 3.55 3.68 La₂O₃ 0.00 0.00 0.00 0.00 0.00 0.00 As₂O₃ 0.25 0.25 0.00 0.25 0.25 0.00 Sb₂O₃ 0.00 0.00 0.00 0.00 0.00 0.00 ZrO₂ 0.00 0.00 0.00 0.00 0.00 0.00 SnO₂ 0.00 0.00 0.00 0.00 0.00 0.00 MgO + La₂O₃ 6.48 4.67 5.27 5.72 4.99 5.37 Sum(RO + La2/3O)* 16.56 16.35 16.85 17.23 16.34 16.85 Sum(RO + La2/3O)/Al₂O₃ 1.41 1.36 1.38 1.40 1.36 1.38 Strain Point (° C.) — — 703 719 — 715 CTE (×10−7/° C.) — — 37.9 38.6 — 37.9 density 2.600 2.642 2.601 2.640 2.623 2.609 Young's modulus (Gpa) — — 81.63 — — 82.12 specific modulus — — 31.4 — — 31.5 200 poise T (° C.) — — 1618 1603 — 1626 Liquidus T (° C.) 1160 1165 1165 1165 1170 1170 Liquidus phase cels anor anor anor cris anor Liquidus Viscosity — — 2.00E+05 1.70E+05 — 2.12E+05 Mol % 47 48 49 50 51 52 SiO₂ 67.53 67.53 67.53 68.38 67.97 68.38 Al₂O₃ 11.77 11.77 11.77 12.04 12.23 12.04 B₂O₃ 3.89 3.89 3.89 2.99 2.90 2.99 MgO 5.49 6.48 6.48 5.84 5.30 6.52 CaO 5.49 4.49 5.49 4.67 5.89 3.27 SrO 4.29 1.90 0.00 1.17 2.04 3.27 BaO 1.30 3.69 4.59 4.67 3.67 3.27 La₂O₃ 0.00 0.00 0.00 0.00 0.00 0.00 As₂O₃ 0.25 0.25 0.25 0.25 0.00 0.25 Sb₂O₃ 0.00 0.00 0.00 0.00 0.00 0.00 ZrO₂ 0.00 0.00 0.00 0.00 0.00 0.00 SnO₂ 0.00 0.00 0.00 0.00 0.00 0.00 MgO + La₂O₃ 5.49 6.48 6.48 5.84 5.30 6.52 Sum(RO + La2/3O)* 16.57 16.56 16.56 16.35 16.90 16.33 Sum(RO + La2/3O)/Al₂O₃ 1.41 1.41 1.41 1.36 1.38 1.36 Strain Point (° C.) 704 — — — 713 — CTE (×10−7/° C.) 38.7 — — — 37.9 — density 2.594 2.621 2.614 2.634 2.606 2.625 Young's modulus (Gpa) — — — — 82.05 — specific modulus — — — — 31.5 — 200 poise T (° C.) 1588 — — — 1628 — Liquidus T (° C.) 1170 1170 1170 1175 1180 1180 Liquidus phase anor cels cels cels anor cels Liquidus Viscosity 1.11E+05 — — — 1.66E+05 — Mol % 53 54 55 56 57 58 SiO₂ 68.76 68.38 68.38 67.53 67.53 68.38 Al₂O₃ 12.26 12.04 12.04 11.77 11.77 12.04 B₂O₃ 2.56 2.99 2.99 3.89 3.89 2.99 MgO 5.35 5.71 6.11 7.38 7.48 6.35 CaO 5.80 4.09 4.09 5.49 3.49 3.63 SrO 1.57 3.27 2.04 0.00 1.90 2.72 BaO 3.70 3.27 4.09 3.69 3.69 3.63 La₂O₃ 0.00 0.00 0.00 0.00 0.00 0.00 As₂O₃ 0.00 0.25 0.25 0.25 0.25 0.25 Sb₂O₃ 0.00 0.00 0.00 0.00 0.00 0.00 ZrO₂ 0.00 0.00 0.00 0.00 0.00 0.00 SnO₂ 0.00 0.00 0.00 0.00 0.00 0.00 MgO + La₂O₃ 5.35 5.71 6.11 7.38 7.48 6.35 Sum(RO + La2/3O)* 16.42 16.34 16.33 16.56 16.56 16.33 Sum(RO + La2/3O)/Al₂O₃ 1.34 1.36 1.36 1.41 1.41 1.36 Strain Point (° C.) 714 — — — — — CTE (×10−7/° C.) 37.9 — — — — — density 2.612 2.627 2.625 2.579 2.606 2.627 Young's modulus (Gpa) 81.63 — — — — — specific modulus 31.3 — — — — — 200 poise T (° C.) 1631 — — — — — Liquidus T (° C.) 1185 1190 1190 1190 1190 1195 Liquidus phase anor Batch cris cris cels cris stone with cris + cels Liquidus Viscosity 1.60E+05 — — — — — Mol % 59 60 61 62 63 64 SiO₂ 68.53 69.53 68.38 68.38 67.63 67.63 Al₂O₃ 12.15 11.95 12.04 12.04 12.15 12.15 B₂O₃ 3.69 3.93 2.99 2.99 3.98 3.98 MgO 6.27 3.12 4.90 4.09 6.87 5.28 CaO 2.99 5.46 4.90 5.71 2.99 5.28 SrO 2.99 3.97 3.27 3.27 2.99 0.00 BaO 2.99 1.80 3.27 3.27 2.99 5.28 La₂O₃ 0.00 0.00 0.00 0.00 0.00 0.00 As₂O₃ 0.40 0.25 0.25 0.25 0.40 0.40 Sb₂O₃ 0.00 0.00 0.00 0.00 0.00 0.00 ZrO₂ 0.00 0.00 0.00 0.00 0.00 0.00 SnO₂ 0.00 0.00 0.00 0.00 0.00 0.00 MgO + La₂O₃ 6.27 3.12 4.90 4.09 6.87 5.28 Sum(RO + La2/3O)* 15.24 14.35 16.34 16.34 15.84 15.84 Sum(RO + La2/3O)/Al₂O₃ 1.25 1.20 1.36 1.36 1.30 1.30 Strain Point (° C.) 709 721 — — 702 694.5 CTE (×10−7/° C.) 36.2 36.9 — — 36.2 38.6 density 2.602 2.571 2.640 2.642 2.610 2.638 Young's modulus (Gpa) — — — — — — specific modulus — — — — — — 200 poise T (° C.) — 1648 — — — — Liquidus T (° C.) 1200 1205 1215 1220 1230 1250 Liquidus phase Sr/Al sil anor anor anor SrSi cels Liquidus Viscosity — 1.22E+05 — — — — Mol % 65 66 67 68 69 70 SiO₂ 69.12 69.43 69.43 68.61 69.22 69.41 Al₂O₃ 12.01 11.88 11.87 12.67 12.21 12.46 B₂O₃ 2.01 2.00 2.00 2.23 2.00 2.00 MgO 5.61 5.55 5.95 5.25 5.42 5.22 CaO 5.61 5.55 4.76 5.59 5.42 5.22 SrO 1.59 0.00 1.19 1.50 1.53 1.48 BaO 4.01 5.55 4.76 3.59 3.73 3.73 La₂O₃ 0.00 0.00 0.00 0.00 0.00 0.00 As₂O₃ 0.00 0.00 0.00 0.00 0.00 0.00 Sb₂O₃ 0.00 0.00 0.00 0.48 0.40 0.40 ZrO₂ 0.02 0.02 0.02 0.00 0.00 0.02 SnO₂ 0.02 0.02 0.02 0.08 0.07 0.07 MgO + La₂O₃ 5.61 5.55 5.95 5.25 5.42 5.22 Sum(RO + La2/3O)* 16.82 16.65 16.66 15.93 16.10 15.65 Sum(RO + La2/3O)/Al₂O₃ 1.40 1.40 1.40 1.26 1.32 1.26 Strain Point (° C.) 733 736 736 728 727 730 CTE (×10−7/° C.) 38.9 38.5 38.0 37.0 37.9 36.8 density 2.630 2.640 2.643 2.637 2.640 2.635 Young's modulus (Gpa) — — — 81.4 81.4 81.4 specific modulus — — — 30.9 30.8 30.9 200 poise T (° C.) 1633 1657 1652 1639 1644 1649 Liquidus T (° C.) 1155 1160 1155 1185 1170 1180 Liquidus phase cels cels cels cels cels cels Liquidus Viscosity 2.60E+05 3.50E+05 4.29E+05 1.98E+05 2.87E+05 2.63E+05 Mol % 71 72 73 74 75 76 SiO₂ 69.38 69.47 69.37 69.77 69.85 69.85 Al₂O₃ 12.44 12.55 13.07 12.87 12.83 12.88 B₂O₃ 1.99 2.00 2.00 2.00 2.00 2.00 MgO 5.21 5.05 5.24 4.93 4.93 4.93 CaO 5.21 5.22 4.81 4.93 4.93 4.93 SrO 1.48 1.47 0.75 1.64 1.40 1.62 BaO 3.72 3.68 4.20 3.30 3.50 3.30 La₂O₃ 0.00 0.00 0.00 0.00 0.00 0.00 As₂O₃ 0.00 0.00 0.00 0.00 0.00 0.00 Sb₂O₃ 0.48 0.47 0.47 0.47 0.47 0.40 ZrO₂ 0.02 0.02 0.02 0.02 0.02 0.02 SnO₂ 0.07 0.07 0.07 0.07 0.07 0.07 MgO + La₂O₃ 5.21 5.05 5.24 4.93 4.93 4.93 Sum(RO + La2/3O)* 15.62 15.42 15.00 14.80 14.76 14.78 Sum(RO + La2/3O)/Al₂O₃ 1.26 1.23 1.15 1.15 1.15 1.15 Strain Point (° C.) 731 729 734 734 738 739 CTE (×10−7/° C.) 37.2 37.3 35.8 36.0 36.1 36.0 density 2.638 2.635 2.642 2.619 2.620 2.615 Young's modulus (Gpa) 80.7 — — — — — specific modulus 30.6 — — — — — 200 poise T (° C.) 1652 1643 1648 1653 1652 1659 Liquidus T (° C.) 1170 1180 1220 1195 1195 1200 Liquidus phase cels cels cels cels cels cels Liquidus Viscosity 2.81E+05 2.47E+05 1.09E+05 1.98E+05 2.04E+05 1.99E+05 Mol % 77 78 79 80 81 82 SiO₂ 70.02 70.61 69.72 69.57 69.39 69.79 Al₂O₃ 12.86 12.59 12.50 12.36 12.22 12.37 B₂O₃ 1.75 1.75 1.93 1.93 1.93 1.70 MgO 4.94 4.83 4.89 4.99 5.09 4.99 CaO 4.94 4.83 5.22 5.32 5.43 5.32 SrO 1.40 1.38 1.46 1.49 1.52 1.49 BaO 3.53 3.45 3.71 3.78 3.86 3.78 La₂O₃ 0.00 0.00 0.00 0.00 0.00 0.00 As₂O₃ 0.00 0.00 0.00 0.00 0.00 0.00 Sb₂O₃ 0.47 0.47 0.49 0.48 0.48 0.48 ZrO₂ 0.02 0.02 0.01 0.00 0.00 0.00 SnO₂ 0.07 0.07 0.07 0.08 0.08 0.08 MgO + La₂O₃ 4.94 4.83 4.89 4.99 5.09 4.99 Sum(RO + La2/3O)* 14.81 14.49 15.28 15.58 15.90 15.58 Sum(RO + La2/3O)/Al₂O₃ 1.15 1.15 1.22 1.26 1.30 1.26 Strain Point (° C.) 735 738 732 721 721 723 CTE (×10−7/° C.) 37.7 35.9 37.2 37.7 39 38.2 density 2.626 2.615 2.638 2.650 2.648 2.652 Young's modulus (Gpa) — 81.4 — — — — specific modulus — 31.1 — — — — 200 poise T (° C.) 1651 1661 1661 — — — Liquidus T (° C.) 1200 1185 1170 1170 1165 1180 Liquidus phase cels Cels cels cels cels cels Liquidus Viscosity 1.81E+05 2.67E+05 2.80E+05 — — — Mol % 83 84 85 86 87 88 SiO₂ 69.62 70.01 69.84 69.36 69.58 69.81 Al₂O₃ 12.22 12.27 12.12 12.05 12.06 12.07 B₂O₃ 1.70 1.70 1.70 1.75 1.50 1.25 MgO 5.09 4.95 5.05 5.35 5.33 5.32 CaO 5.43 5.28 5.39 5.54 5.56 5.58 SrO 1.52 1.48 1.51 1.51 1.51 1.50 BaO 3.86 3.75 3.83 3.96 3.98 3.99 La₂O₃ 0.00 0.00 0.00 0.00 0.00 0.00 As₂O₃ 0.00 0.00 0.00 0.00 0.00 0.00 Sb₂O₃ 0.48 0.48 0.48 0.39 0.39 0.39 ZrO₂ 0.00 0.00 0.00 0.02 0.02 0.02 SnO₂ 0.08 0.08 0.08 0.07 0.07 0.07 MgO + La₂O₃ 5.09 4.95 5.05 5.35 5.33 5.32 Sum(RO + La2/3O)* 15.90 15.46 15.78 16.36 16.38 16.39 Sum(RO + La2/3O)/Al₂O₃ 1.30 1.26 1.30 1.36 1.36 1.36 Strain Point (° C.) 726 728 725 — — — CTE (×10−7/° C.) 38.1 37.7 36.9 — — — density 2.648 2.634 2.633 — — — Young's modulus (Gpa) — — — — — — specific modulus — — — — — — 200 poise T (° C.) — — — — — — Liquidus T (° C.) 1175 1170 1160 — — — Liquidus phase cels Cels cels — — — Liquidus Viscosity — — — — — — *Sum(RO + La2/3O) = Sum(RO + 3La₂O₃)

TABLE 2 Glass A Glass B Glass C strain point 716° C. 725° C. 667° C. Time (min) Compaction (ppm) 0 0 0 0 5 −12 −16 −43 10 −20 −23 −74 15 −26 −31 −91 30 −40 −45 −137 60 −61 −62 −202 120 −94 −87 −270 180 −110 −108 Not measured 240 −128 −125 −359 300 −144 −141 −383 

What is claimed is:
 1. An alkali metal-free glass comprising in mole percent on an oxide basis: SiO₂ 65.0-72.0 Al₂O₃  9.0-16.0 B₂O₃ 1.0-5.0 MgO + La₂O₃ 1.0-7.5 CaO 2.0-6.0 BaO 1.0-7.0

wherein: (i) when the glass comprises the optional component SrO, the glass satisfies the relationship: [BaO]/[SrO]≧2.0, where [BaO] and [SrO] represent the mole percents of BaO and SrO, respectively, (ii) the glass has a strain point greater than or equal to 700° C., and (iii) the glass exhibits a dimensional change of less than 30 ppm for a 5 minute heat treatment at 600° C.
 2. A liquid crystal display substrate comprising the glass of claim
 1. 3. The glass of claim 1 wherein the glass has a liquidus viscosity greater than or equal to 150,000 poise.
 4. A method for producing alkali metal-free glass sheets by a downdraw process comprising selecting, melting, and fining batch materials so that the glass making up the sheets has the composition of claim 1, wherein: (a) the fining is performed without the use of substantial amounts of arsenic; and (b) a population of 50 sequential glass sheets produced by the downdraw process from the melted and fined batch materials has an average gaseous inclusion level of less than 0.10 gaseous inclusions/cubic centimeter, where each sheet in the population has a volume of at least 500 cubic centimeters.
 5. The method of claim 4 wherein the downdraw process comprises a fusion draw process.
 6. The method of claim 4 further comprising using the glass sheets as substrates for liquid crystal displays.
 7. The method of claim 4 wherein the glass making up the sheets has a liquidus viscosity greater than or equal to 150,000 poise.
 8. An alkali metal-free glass comprising in mole percent on an oxide basis: SiO₂ 65.0-72.0 Al₂O₃  9.0-16.0 B₂O₃ 1.0-5.0 MgO + La₂O₃ 1.0-7.5 CaO 3.0-6.0 SrO 0.0-4.5 BaO 1.0-7.0

wherein: (i) the glass has a strain point greater than or equal to 710° C., (ii) the glass exhibits a dimensional change of less than 30 ppm for a 5 minute heat treatment at 600° C., and (iii) the glass has a melting temperature that is less than or equal to 1,665° C., where the melting temperature is the temperature at which the glass has a viscosity of 200 poise.
 9. A liquid crystal display substrate comprising the glass of claim
 8. 10. The glass of claim 8 wherein the glass has a liquidus viscosity greater than or equal to 150,000 poise.
 11. A method for producing alkali metal-free glass sheets by a downdraw process comprising selecting, melting, and fining batch materials so that the glass making up the sheets has the composition of claim 8, wherein: (a) the fining is performed without the use of substantial amounts of arsenic; and (b) a population of 50 sequential glass sheets produced by the downdraw process from the melted and fined batch materials has an average gaseous inclusion level of less than 0.10 gaseous inclusions/cubic centimeter, where each sheet in the population has a volume of at least 500 cubic centimeters.
 12. The method of claim 11 wherein the downdraw process comprises a fusion draw process.
 13. The method of claim 11 further comprising using the glass sheets as substrates for liquid crystal displays.
 14. The method of claim 11 wherein the glass making up the sheets has a liquidus viscosity greater than or equal to 150,000 poise. 